U.S. patent application number 16/680199 was filed with the patent office on 2020-03-12 for multicomponent compositions for mercury removal.
The applicant listed for this patent is ENVIRONMENTAL ENERGY SERVICES, INC.. Invention is credited to Thomas K. Gale.
Application Number | 20200078727 16/680199 |
Document ID | / |
Family ID | 51659025 |
Filed Date | 2020-03-12 |
United States Patent
Application |
20200078727 |
Kind Code |
A1 |
Gale; Thomas K. |
March 12, 2020 |
MULTICOMPONENT COMPOSITIONS FOR MERCURY REMOVAL
Abstract
Herein are disclosed compositions of matter, processes of
manufacture and processes of use of solid state admixtures that
include an inorganic base and a sulfide selected from the group
consisting of an ammonium sulfide, an alkali metal sulfide, an
alkali-earth metal sulfide, transition metal sulfide, and a mixture
thereof. The composition can include solid state inorganic bases
(e.g., calcium hydroxide and sodium sesquicarbonate) and/or gaseous
bases (e.g., ammonia) and, optionally, a support material for one
or more of the inorganic base and sulfide. The compositions are
useful for capturing environmental contaminants, for example, from
the flue gas of a coal fired power plant.
Inventors: |
Gale; Thomas K.; (Highlands
Ranch, CO) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ENVIRONMENTAL ENERGY SERVICES, INC. |
Sandy Hook |
CT |
US |
|
|
Family ID: |
51659025 |
Appl. No.: |
16/680199 |
Filed: |
November 11, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14774254 |
Sep 10, 2015 |
10471385 |
|
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PCT/US2014/023989 |
Mar 12, 2014 |
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16680199 |
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61778778 |
Mar 13, 2013 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B01D 15/08 20130101;
B01D 2251/306 20130101; B01J 20/10 20130101; B01J 20/045 20130101;
B01J 20/08 20130101; B01D 2257/30 20130101; B01D 2251/608 20130101;
B01D 53/40 20130101; B01J 20/20 20130101; B01D 2258/0283 20130101;
B01D 2253/304 20130101; B01J 2220/42 20130101; B01J 20/041
20130101; B01D 2251/604 20130101; B01D 53/81 20130101; B01J 20/16
20130101; B01D 53/64 20130101; B01D 2251/304 20130101; B01D
2251/404 20130101; B01D 53/508 20130101; B01J 20/3293 20130101;
B01D 53/02 20130101; B01D 2253/11 20130101; B01J 20/3007 20130101;
B01J 20/043 20130101; B01J 20/3021 20130101; B01J 20/3028 20130101;
B01D 2251/606 20130101; B01J 20/02 20130101; B01D 2257/602
20130101; B01J 20/0285 20130101 |
International
Class: |
B01D 53/64 20060101
B01D053/64; B01D 53/02 20060101 B01D053/02; B01J 20/04 20060101
B01J020/04; B01J 20/10 20060101 B01J020/10; B01J 20/20 20060101
B01J020/20; B01J 20/02 20060101 B01J020/02; B01D 15/08 20060101
B01D015/08; B01D 53/40 20060101 B01D053/40; B01D 53/81 20060101
B01D053/81; B01J 20/08 20060101 B01J020/08; B01J 20/16 20060101
B01J020/16; B01D 53/50 20060101 B01D053/50; B01J 20/32 20060101
B01J020/32; B01J 20/30 20060101 B01J020/30 |
Claims
1. A composition comprising: a solid state admixture of an
inorganic base and a sulfide selected from the group consisting of
an ammonium sulfide, an alkali metal sulfide, an alkali-earth metal
sulfide, transition metal sulfide, and a mixture thereof.
2. The composition of claim 1 consisting essentially of an
admixture of the inorganic base and the sulfide.
3. The composition of claim 1 further comprising a support carrying
the admixture.
4. The composition of claim 3, wherein the composition consists
essentially of the support carrying the admixture.
5. The composition of claims 3-4, wherein the support is selected
from the group consisting of a silicate, an aluminate, an
aluminosilicate, a carbon, and a mixture thereof.
6. The composition of any one of claims 3-5, wherein the support is
a phyllosilicate selected from the group consisting of bentonite,
montmorillonite, hectorite, beidellite, saponite, nontronite,
volkonskoite, sauconite, stevensite, fluorohectorite, laponite,
rectonite, vermiculite, illite, a micaceous mineral, makatite,
kanemite, octasilicate (illierite), magadiite, kenyaite,
attapulgite, palygorskite, sepoilite, and a mixture thereof.
7. The composition of any one of the preceding claims, wherein the
inorganic base is selected from the group consisting of calcium
hydroxide, sodium sesquicarbonate (trisodium hydrogendicarbonate),
sodium carbonate, sodium bicarbonate, potassium carbonate, calcium
carbonate, and a mixture thereof.
8. The composition of claim 7, wherein the inorganic base is
selected from the group consisting of calcium hydroxide, sodium
sesquicarbonate, and a mixture thereof.
9. The composition of any one of the preceding claims, wherein the
sulfide is a polysulfide.
10. The composition of any one of the preceding claims, wherein the
sulfide is a transition metal sulfide selected from the group
consisting of a manganese sulfide, an iron sulfide, a cobalt
sulfide, a nickel sulfide, a copper sulfide, a zinc sulfide, and a
mixture thereof.
11. The composition of any one of claims 3-10, wherein the
inorganic base is a calcium hydroxide, the sulfide is a copper
sulfide and the support is selected from the group consisting of
bentonite and montmorillonite.
12. The composition of any one of claims 3-10, wherein the
inorganic base is a calcium hydroxide, the sulfide is an alkali
metal sulfide and the support is selected from the group consisting
of bentonite and montmorillonite.
13. The composition of any one of claims 3-10, wherein the
inorganic base is sodium sesquicarbonate, the sulfide is a copper
sulfide and the support is selected from the group consisting of
bentonite and montmorillonite.
14. The composition of any one of claims 3-10, wherein the
inorganic base is sodium sesquicarbonate, the sulfide is an alkali
metal sulfide and the support is selected from the group consisting
of bentonite and montmorillonite.
15. The composition of any one of claim 3-14, wherein the admixture
is distributed on the surface of the support.
16. The process of capturing an environmental contaminant from a
fluid, the process comprising: admixing a fluid containing an
environmental contaminant with the composition of any one of claim
1-15; and separating the fluid and the composition; wherein the
separated fluid includes a lower concentration of the environmental
contaminant after separation from the composition.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. application Ser.
No. 14/774,254, filed Sep. 10, 2015, entitled "Multicomponent
Compositions for Mercury Removal," which is a national stage
application under 35 U.S.C. .sctn. 371 of International Application
No. PCT/US2014/023989, filed Mar. 12, 2014, entitled
"Multicomponent Compositions for Mercury Removal," which claims
priority to U.S. Provisional Patent Application No. 61/778,778,
filed Mar. 13, 2013, the contents of all of which are hereby
incorporated herein in their entirety by reference for all
purposes.
FIELD OF THE INVENTION
[0002] The present invention is directed to methods of using
compositions for removing one or more environmental contaminant(s)
(e.g., mercury or sulfur) from gas streams, e.g., industrial smoke
stacks; flue ducts, and the like. The compositions, "flue gas
scrubbing compositions", are particularly useful for removal of
mercury from the flue gas emitted by coal-burning electrical power
plants.
BACKGROUND
[0003] Environmental contaminants contained in emissions from
coal-fired and oil-fired power plants are a major environmental
concern. Particulate matter (e.g., fly ash), nitrates, sulfates,
and mercury emissions are restricted because these emissions can
yield, for example, acid rain and serious neurotoxic effects. The
removal of particulate matter has been addressed through the
installation of baghouses, electrostatic precipitators, cyclone
separators, or cyclone separators with baghouse filters in the flue
gas ducts. The removal of nitrates and sulfates has been addressed
through the addition of lime (calcium oxides and/or hydroxides) to
the flue gas and the collection of the lime reaction product (e.g.,
CaSO.sub.4) with the particulate matter. The removal of mercury can
be addressed by absorption with a mercury absorbent material.
Unfortunately, the mercury absorbent materials and lime are often
chemically incompatible and/or the mercury absorbent material is
fiscally incompatible with the collection and disposal of the
particulate material which is often sold into the concrete
industry.
[0004] The most common method for reduction of mercury emissions
from coal-fired and oil-fired power plants is the injection of
powdered, activated carbon into the flue gas stream. The activated
carbon is a high surface area material that provides for the
adsorption of the mercury and the agglomeration of the particle
bound mercury. The disadvantage of adding activated carbon into the
flue gas stream is the retention of the activated carbon in the fly
ash waste stream. Fly ash from coal-fired power plants is often
added to concrete, where the presence of the activated carbon
adversely affects performance, thereby making the inclusion of the
carbon fiscally incompatible with the flue gas scrubbing
process.
[0005] Another method for reducing Hg emissions is through the
addition of chemical species that react with mercury to chem-adsorb
the elemental and oxidized mercury. One class of materials capable
of chemically reacting with Hg is metal sulfides. U.S. Pat. Nos.
6,719,828 and 7,578,869 teach the preparation of supported metal
sulfides. A major disadvantage of these supported metal sulfides is
that these materials are known to react with lime, for example,
yielding copper metal and calcium sulfide materials. See e.g.,
Habashi et al., Metallurgical Transactions, 1973, 4, 1865. These
reaction products destroy the absorptive capacity of mercury from
the flue gas. Therefore, the use of supported metal sulfides has
been physically separated from the use of lime in the flue gas
scrubbing process.
[0006] There is still an ongoing need to provide improved pollution
control sorbents and methods of their manufacture, particularly
sorbents that are stable both in acidic flue gases and in the
presence of acid reducing species.
SUMMARY
[0007] One embodiment is a composition that includes a solid state
admixture of an inorganic base and a sulfide selected from the
group consisting of an ammonium sulfide, an alkali metal sulfide,
an alkali-earth metal sulfide, transition metal sulfide, and a
mixture thereof.
[0008] Another embodiment is a manufacturing process that includes
providing the solid state admixture by intimately mixing the
inorganic base and the sulfide.
[0009] Still another embodiment is a process of capturing an
environmental contaminant from a fluid, the process that includes
admixing a fluid containing an environmental contaminant with the
composition that includes the solid state admixture; and separating
the fluid and the composition; wherein the separated fluid includes
a lower concentration of the environmental contaminant after
separation from the composition.
[0010] Yet another embodiment is a composition that includes an
admixture of anhydrous ammonia and a supported sulfide, the
supported sulfide comprising a sulfide selected from the group
consisting of an alkali metal sulfide, an alkali-earth metal
sulfide, transition metal sulfide, and a mixture thereof, and a
support selected from the group consisting of a silicate, an
aluminate, an aluminosilicate, a carbon, and a mixture thereof.
[0011] Still yet another embodiment is a process of capturing an
environmental contaminant from a fluid, the process includes
admixing a fluid containing an environmental contaminant with
anhydrous ammonia; admixing the fluid containing the environmental
contaminant with a supported sulfide; and admixing the anhydrous
ammonia and the supported sulfide in the fluid; wherein the
supported sulfide comprises a sulfide selected from the group
consisting of an alkali metal sulfide, an alkali-earth metal
sulfide, transition metal sulfide, and a mixture thereof, and a
support selected from the group consisting of a silicate, an
aluminate, an aluminosilicate, a carbon, and a mixture thereof.
[0012] Another embodiment is a process of capturing an
environmental contaminant from a fluid, the process includes
admixing anhydrous ammonia and a supported sulfide to provide a
composition; and admixing the composition with the fluid containing
an environmental contaminant; wherein the supported sulfide
comprises a sulfide selected from the group consisting of an alkali
metal sulfide, an alkali-earth metal sulfide, transition metal
sulfide, and a mixture thereof, and a support selected from the
group consisting of a silicate, an aluminate, an aluminosilicate, a
carbon, and a mixture thereof.
DETAILED DESCRIPTION
[0013] A first embodiment is a composition that includes a solid
state admixture of an inorganic base and a sulfide selected from
the group consisting of an ammonium sulfide, an alkali metal
sulfide, an alkali-earth metal sulfide, transition metal sulfide,
and a mixture thereof. In one preferable example, the composition
includes a support carrying the admixture. Preferably, the support
is selected from the group consisting of a silicate, an aluminate,
an aluminosilicate, a carbon, and a mixture thereof. For example,
the support can be a phyllosilicate selected from the group
consisting of bentonite, montmorillonite, hectorite, beidellite,
saponite, nontronite, volkonskoite, sauconite, stevensite,
fluorohectorite, laponite, rectonite, vermiculite, illite, a
micaceous mineral, makatite, kanemite, octasilicate (illierite),
magadiite, kenyaite, attapulgite, palygorskite, sepoilite, and a
mixture thereof. The support can be a smectite clay e.g.,
bentonite, montmorillonite, hectorite, beidellite, saponite,
nontronite, volkonskoite, sauconite, stevensite, and/or a synthetic
smectite derivative, particularly fluorohectorite and laponite; a
mixed layered clay, particularly rectonite and their synthetic
derivatives; vermiculite, illite, micaceous minerals, and their
synthetic derivatives; layered hydrated crystalline polysilicates,
particularly makatite, kanemite, octasilicate (illierite),
magadiite and/or kenyaite; attapulgite, palygorskite, sepoilite; or
any combination thereof. The support can be an activated carbon, a
powder activated carbon, a graphite, or a mixture thereof. More
preferably, the admixture is distributed on the surface of the
support.
[0014] In a preferred example, the support carries the admixture.
Herein this means the support is in intimate contact with each
individual component of the admixture (e.g., the inorganic base
and, individually, the sulfide). In one instance, a portion of the
inorganic base and a portion of the sulfide are supported on a
support particulate. That is, the support is preferable a
particulate material (e.g., consists of a plurality of distinct
particles) and, in this instance, a single particulate carries both
the inorganic base and the sulfide. Notably, the inorganic base
and/or the sulfide can be particulates, preferably, having a
particle diameter less than 25%, 20%, 15%, or 10% of a particle
diameter of the support. In another instance, the inorganic base
and the sulfide can be carried on distinct supports. For example, a
plurality of particles of the support can carry the inorganic base
and a plurality of particles of the support can carry the sulfide.
In a subset of this instance, the support carrying the inorganic
based is distinct from the support carrying the sulfide, the
distinction can be in particle size, composition, or a combination
thereof. Still further, the composition can include an admixture of
a plurality of particles where two are selected from the group
consisting of the support carrying the inorganic base, the support
carrying the sulfide, and the support carrying both the inorganic
based and the sulfide.
[0015] The solid state admixture of an inorganic base and a sulfide
can include distinct phases, regions or particulates of each of the
inorganic base and sulfide and/or can include the reaction product
of the inorganic base and the sulfide. In a preferable instance,
the admixture includes distinct phases, regions or particulates
(e.g., crystallites) of the inorganic base and the sulfide. In
instances wherein the admixture consist of or consist essentially
of distinct phases, regions or particulates of the inorganic base
and sulfide, the inorganic base can carry the sulfide and/or the
sulfide can carry the inorganic base. Examples include core-shell
arrangements and agglomerations of smaller particulates upon a
larger particulate.
[0016] In one instance, the inorganic base can be selected from the
group consisting of calcium hydroxide, sodium sesquicarbonate
(trisodium hydrogendicarbonate), sodium carbonate, sodium
bicarbonate, potassium carbonate, calcium carbonate, and a mixture
thereof. Preferably, the inorganic base is selected from calcium
hydroxide and sodium sesquicarbonate. In one example, the inorganic
base is calcium hydroxide (e.g., hydrated lime); in another
example, the inorganic base is sodium sesquicarbonate (e.g.,
trona).
[0017] The calcium hydroxide can be hydrated lime; hydrated lime is
a dry powder manufactured by treating quicklime with sufficient
water to satisfy its chemical affinity for water, thereby
converting the oxides to hydroxides. Depending upon the type of
quicklime used and the hydrating conditions employed, the amount of
water in chemical combination varies, for example: high calcium
hydrated lime contains generally 72% to 74% calcium oxide and 23%
to 24% chemically combined water; dolomitic hydrated lime (normal)
contains about 46% to 48% calcium oxide, 33% to 34% magnesium
oxide, and 15% to 17% chemically combined water; dolomitic hydrated
lime (pressure) contains about 40% to 42% calcium oxide, 29% to 30%
magnesium oxide, and 25% to 27% chemically combined water.
[0018] The sulfide can be a terminal or bridged sulfide (i.e.,
S.sup.2-); can be a polysulfide (e.g., S.sub.2.sup.2-,
S.sub.3.sup.2-, S.sub.4.sup.2-, S.sub.n.sup.2-); can be a thiolate
(i.e., SH.sup.-, SR.sup.-); or can be a hydropolysulfide (e.g.,
S.sub.2H.sup.-). In one example, the sulfide is a polysulfide. In
an example, the sulfide can be a transition metal sulfide selected
from the group consisting of a manganese sulfide, an iron sulfide,
a cobalt sulfide, a nickel sulfide, a copper sulfide, a zinc
sulfide, and alloy thereof, and a mixture thereof.
[0019] In another instance, the composition can be described as a
sulfide modified support carrying the inorganic base. For example,
the composition include a support modified with a transition metal
sulfide (e.g., manganese sulfide, iron sulfide, cobalt sulfide,
nickel sulfide, copper sulfide, zinc sulfide, alloys thereof, and
mixture thereof) where the modified support carries the inorganic
base (e.g., trona and/or calcium hydroxide).
[0020] In one specific example, the inorganic base is a calcium
hydroxide, the sulfide is a copper sulfide and the support is
selected from the group consisting of bentonite and
montmorillonite. In another specific example, the inorganic base is
a calcium hydroxide, the sulfide is an alkali metal sulfide and the
support is selected from the group consisting of bentonite and
montmorillonite. In yet another specific example, the inorganic
base is sodium sesquicarbonate, the sulfide is a copper sulfide and
the support is selected from the group consisting of bentonite and
montmorillonite. In still another specific example, the inorganic
base is sodium sesquicarbonate, the sulfide is an alkali metal
sulfide and the support is selected from the group consisting of
bentonite and montmorillonite.
[0021] Another embodiment is a process for manufacturing the above
described compositions. The process can include providing the solid
state admixture by intimately mixing the inorganic base and the
sulfide. The intimate mixing can be provided by a process selected
from the group consisting of ball milling, extruding, solid state
mixing, grinding, coprecipitation, and a mixture thereof. The
intimate mixing, preferably, includes reducing particle diameters
of the inorganic base in the presence of the sulfide and/or
reducing particle diameters of the sulfide in the presence of the
inorganic base. Preferably, the process includes intimately mixing
the inorganic base and the sulfide with a support; and when the
support is included, the intimately mixing includes reducing the
particle diameter of the support.
[0022] Still another embodiment is a process of capturing an
environmental contaminant from a fluid employing the above
described compositions. The process can include admixing a fluid
containing an environmental contaminant with the above described
composition, and then separating the fluid and the composition. The
separated fluid preferably includes a lower concentration of the
environmental contaminant after separation from the composition.
Notably, the fluid can be a liquid or a gas. In one example the
fluid is the flue gas produced by the combustion of coal. In
another example, the fluid is a wet scrubber's discharge
liquor.
[0023] The environmental contaminant can be mercury, selenium,
lead, chromium, arsenic, cadmium, and a mixture thereof.
Preferably, the described compositions separate mercury from the
fluid.
[0024] In still yet another embodiment, a composition can include
an admixture of anhydrous ammonia and a supported sulfide. The
supported sulfide includes at least a sulfide selected from the
group consisting of an alkali metal sulfide, an alkali-earth metal
sulfide, transition metal sulfide, and a mixture thereof, and a
support selected from the group consisting of a silicate, an
aluminate, an aluminosilicate, a carbon, and a mixture thereof. In
one example, the admixture includes ammonium cations formed by a
reaction of the anhydrous ammonia with the support. In another
example, the admixture includes ammonia adhered to the surface of
the supported sulfide.
[0025] In yet another embodiment, a process of capturing an
environmental contaminant from a fluid can include admixing a fluid
containing an environmental contaminant with anhydrous ammonia;
admixing the fluid containing the environmental contaminant with a
supported sulfide; and admixing the anhydrous ammonia and the
supported sulfide in the fluid. The supported sulfide includes at
least a sulfide selected from the group consisting of an alkali
metal sulfide, an alkali-earth metal sulfide, transition metal
sulfide, and a mixture thereof, and a support selected from the
group consisting of a silicate, an aluminate, an aluminosilicate, a
carbon, and a mixture thereof.
[0026] In still another embodiment, a process of capturing an
environmental contaminant from a fluid can include admixing
anhydrous ammonia and a supported sulfide to provide a composition;
and admixing the composition with the fluid containing an
environmental contaminant. The supported sulfide includes at least
a sulfide selected from the group consisting of an alkali metal
sulfide, an alkali-earth metal sulfide, transition metal sulfide,
and a mixture thereof, and a support selected from the group
consisting of a silicate, an aluminate, an aluminosilicate, a
carbon, and a mixture thereof.
[0027] The foregoing description is given for clearness of
understanding only, and no unnecessary limitations should be
understood therefrom, as modifications within the scope of the
invention may be apparent to those having ordinary skill in the
art.
* * * * *